3,3,3&#39;,3&#39;-tetramethyl-6,6&#39;-di(2-hydroxypropoxy)- 1,1&#39;-spirobiindane



United States Patent 3,544,638 3,3,3,3'-TETRAMETHYL-6,6-DI(2-HYDROXY-PROPOXY)-1,1'-SPIROBIINDANE Erkki J. Pulkkinen, Morris Plains, N.J.,assignor to Allied Chemical Corporation, New York, N.Y., a corporationof New York No Drawing. Filed Dec. 13, 1968, Ser. No. 783,721 Int. Cl.C07c 43/26 US. Cl. 260-613 1 Claim ABSTRACT OF THE DISCLOSURE Thisinvention relates to the propoxylation of 3,3,3',3'- tetramethyl 6,6dihydroxy-1,1-spirobiindane to form 3,3,3,3 tetramethyl6,6'-di(2-hydroxypropoxy)-1,1- spirobiindane and to the reaction of thislatter compound with an ethylenically unsaturated dicarboxylic acid togive an unsaturated polyester. These unsaturated polyesters can becross-linked with styrene to give a cured polyester having excellentchemical resistance which is useful in films, molded articles and inreinforced sheets such as polyester impregnated glass fabric.

In accordance with the present invention3,3,3',3'-tetramethyl-6,6-dihydroxy-l,l-spirobiindane is reacted withpropylene oxide to give 3,3,3',3'-tetramethyl-6,6-di(2-hydroxypropoxy)-l,1-spir0biindane as illustrated by the followingequation:

The reaction temperature is preferably about 50-150 C. The reaction canbe conveniently carried out in a solvent medium such as an alkanol of1-3 carbon atoms, tetrahydrofuran, dimethyl sulfoxide, Carbitol, butylCarbitol, sulfolane and methyl-, ethyland butyl Cellosolve. The reactioncan be catalyzed by the presence of certain bases includingtriethanolamine and alkali metal alkoxide such as sodium and potassiummethoxide and propoxide. Preferably about 2-10 moles of propylene oxideare employed per mole of 3,3,3,3'-tetramethy1 6,6 dihydroxy-1,1'-spirobiindane.

The 3,3,3',3' tetramethyl-6,6-di(2-hydroxypropoxy)- 1,1'-spirobiindanecan be reacted with an acidic compound, i.e., fumaric acid, maleic acid,or maleic anhy- CH, coon CH=CH COOH HCH

HOHCOHzO e OCHzCHOCOCH=CHCO-O This reaction is preferably carried out ata temperature of ISO-240 C. An excess of either reactant can be used butapproximately equimolar amounts of3,3,3',3'-tetramethyl-6,6'-di(Z-hydroxypropoxy)-1,1'-spirobiindane andthe acidic compound are preferred. A portion of the 3,3,3,3 tetramethyl6,6 di(2-hydroxypropoxy)-1,1- spirobiindane can be replaced with anotherbisphenol compound. For instance, useful polyesters can be prepared byreplacing up to of the 3,3,3',3'-tetramethyl6,6-di(Z-hydroxypropoxy)-1,1'-spirobiindane with 2,2-bis(4-hydroxypheny1) propane, which has been propoxylated as above.

The unsaturated polyesters can be cured or crosslinked with anunsaturated monomer such as styrene to give a cured polymer useful infilms and molded articles. Additionally, the polyester can beimpregnated onto a reinforced material such as glass fabric and thencured to give a structural material useful in boat hulls, buildingmaterials, etc. In curing the polyester a peroxide catalyst such asbenzoyl peroxide is generally used. The cured polyesters of thisinvention are characterized by excellent chemical resistance to suchmaterials as gasoline, ammonia, water and sulfuric acid.

The following examples are given to further illustrate the invention butit is to be understood that the invention is not to be limited to thedetails disclosed therein.

EXAMPLE 1 Propylene oxide (92.9 grams) was dissolved in 250 ml. of ethylalcohol containing 3.85 grams of sodium methoxide and grams of3,3,3',3'-tetramethyl-6,6'- dihydroxy-l,l'-spirobiindane. An additional390 ml. of ethanol were then added and the reaction mixture heated atabout 70-80 C. for 2 and /2 hours. The reaction mixture was cooled anddiluted with Water to precipitate a white crystalline product. Thisprecipitate was recovered by filtration and dried in an oven at C. Therewas thus obtained 133.5 grams of 3,3,3,3'-tetramethyl-6,6-di(2-hydroxypropoxy)-1,1-spirobiindane having a melting point of 201 C.

EXAMPLE 2 A mixture of 256 grams of 3,3,3,3'-tetramethyl-6,6'-di(2-hydroxypropoxy)-1,1'-spirobiindane, 69.5 grams of fumaric acid and0.27 gram of hydroquinone were stirred 3 in mesitylene under a nitrogenatmosphere for one hour at 178198 C. The temperature was then raised to200 C. for 6 hours and then to 210 C. for 6 hours. Vacuum (18 mm. Hg)was then applied and heating continued for 3 /2 hours. The reactionproduct was dissolved in methylene chloride, solid material removed byfiltration and the filtrate evaporated to dryness. The product recoveredafter removal of the methylene chloride solvent was the polyester of3,3,3',3'-tetramethyl-6,6'-di(Z-hydroxypropoxy)-1,l'-spirobiindane andfumaric acidhaving an acid number of 9.19 and a hydroxy number of 53.

EXAMPLE 3 2,2 bis (4 hydroxyphenyl) propane was propoxylated using themethod of Example 1 to form 2,2-bis[4,4'-(hydroxypropoxy)phenyl]propane.

The procedure of Example 2 was repeated using 153 grams of3,3,3,3'-tetramethyl6,6'-di(2-hydroxypropoxy)- 1,1-spirobiindane, 153grams of the propoxylated 2,2-bis (4-hydroxyphenyl)propane, 93.3 gramsof fumaric acid and 0.36 grams hydroquinone. The polyester obtained hadan acid number of 13.4 and a hydroxyl number of 13.4.

EXAMPLE 4 Samples (400 grams) of the polyesters of Examples 2 and 3 wereeach dissolved in 490 grams of styrene. Benzoyl peroxide grams) wasadded to each of the solutions and the solutions cured between glassplates at 120 F. for 24 hours and then at 245 F. for 2% hours. There wasthus obtained 2 sheets of cured polyester resin. Samples of these sheetswere placed in test solutions to determine their chemical resistance.The results of these tests with polyester A being derived from thepolyester of Example 2 and polyester B being derived from the polyesterof Example 3 are as follows.

TABLE I Percent change in weight Polyester Test 1 week 1 month 3 months.A 25% NH at 90 F 1.7 B -.do 2. 32

Ethyl gasoline at 90 F 0 10 0. 19 0.42 B do 0. 26 0. 46 0. 70 A- Waterat 158 F 0. 43 0. 43 0. 45 B do 0. 51 0. 44 0. 16 A 5% NaOH at 158 F0.47 O. 40 0. 42 13-..- do 0.48 0.31 0 01 A 5% H280 at 158 F 0. 48 0. 480. 50 B do 0. 43 0. 43 0. 08

FOREIGN PATENTS 1/1957 France 260--213 OTHER REFERENCES Journal Chem.Soc. (London) (1962), p. 415. Journal of Polymer Science, vol. 3 (1965),pp. 3209- 3217.

BERNARD HELFIN, Primary Examiner US. Cl. X.R.

